Spinning process



Patented May 20, 1941 UNITED STATES TEN SPINNING PROCESS Rudolph S. Bley, Elizabethton, Tenn, assignor to North American Rayon Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 2, 1931,

Serial No. 177,822

13 Claims.

In the manufacture of cellulosic products, such as filaments, threads, and the like, a viscose solution is continuously extruded through the minute orifices of a spinneret into a coagulating or setting bath (spin bath). However, since the introduction of the viscose process great troubles have been and are still experienced as far as continuous spinning is concerned due to impurities, such as, for example, precipitated cellulose particles, sulphur and resin particles, zinc compounds, etc., present in either the viscose solution or the spin bath. These impurities gradually contaminate the spinnerets, clog' and reduce or more carbon atoms with an organic sulphide,

selected from the group consisting of dialkyl sulphides, diaryl sulphides and alkyl-aryl. sulphides under substantially anhydrous conditions.

Petroleum consists of complex mixtures of hydrocarbons concerning the chemical nature of which there is very little information, although there are indications that all of these materials contain members of the methane series, the polymethylene series and the benzene series of hydrocarbons. The difference between petroleums of various sources resides in the proportions of the difierent types of hydrocarbons and in the chemical nature and amounts of their impurities. Pennsylvania oil, for example, contains a large proportion of methane hydrocarbons and practically no impurities of sulphur or nitrogen compounds. About thirty hydrocarbons have been isolated and identified with certainty. Distillation is the principal method in separating petroleum into useful components. The distilled fractions from crude petroleum are casinghead gasoline, gasoline, kerosene, gas oil and lighter lubricating oils (neutrals). The residues from such distillation supply most of the lubricatingv oils (bright stock"), petrolatum in pasty or liquid form and either paraffin wax of the crude petroleum. Kerosene is any mixture of hydrocarbons which is not volatile enough for use in explosion motors. Cracked gasolines are rich in olefins and diolefins. Paraflln wax was originally obtained from tars from the distillation'ofwo'od, peat, and lignite, but is now obtained from petroleum, and especially from Pennsylvania paramn-base oils. Little information is available about the composition of paraffin waxes except that it consists mainly of higher alkanes and only small amounts of the normal compounds. Petrolatum (vaseline) is a pasty mixture of hydrocarbons similar to paraflin whil liquid petrolatum is a high boiling petroleum l5 distillate. Ozokerite is a natural paraffin wax originating in Galicia; in bleached form it is termed ceresin. All of these petroleum hydrocarbons may be halogenated in conventional manner in the presence or absence of catalysts 20 to form halogenated hydrocarbon mixtures adapted to be condensed with the tertiary bases and organic sulphides, set forth above. The materials, i. e., crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflin waxes, to be halogenatedmay first be dissolved in carbon tethachloride, etc., and subsequently chlorine, bromine, etc., in gaseous form introduced therein until the heat of reaction abates. Halogenated compounds, containing about 25 to 40% of halogen may be obtained in this manner. However, upon prolonging the introduction of halogens, compounds may .be obtained containing up to about 75% of a halogen, and it is to be noted that the boiling or fusing points of the raw materials are either lowered or raised by halogenation. Hydrochlorlc acid, hydrobromic acid, etc., formed during this reaction must be removed, preferably by neutralization. Catalysts, such as iron, etc., may

be added tothe mixtures to accelerate halogenation. Halogenation will also proceed more rapidly by carrying out the reaction under the influence of ultraviolet rays. The halogenatlon may also be performed in accordance with processes disclosed, for example, in U. 5. Patent #989,225 to Blakeman of April 11, 1911; U. S. Patent #l,246,810 to Ellis of November 13, 1917; U. S. Patent #1,432,'761 to Koch of October 24,

1922; ,etc. Chlorinated paraiiin wax, sold under the tradename of Chlorafin is a very suitable raw material for my process.

Organic sulphides capable of being condensed with the halogenated, hydrocarbonaceous maor petroleum pitch, depending upon the nature 35f terials set forth above are dialkvl sulphides,

extended hydrocarbon chain (fat chain).

diaryl sulphides and alkyl-aryl sulphides, having the following structure:

in which R1 and R: represent monovalent aliphatic (alkyl) or aromatic (aryl) radicals. Examples of such organic sulphides are dimethyl sulphide, diethyl sulphide, methyl-ethyl sulphide, methyl-propyl sulphide, dibutyl sulphide, methyl-benzyl sulphide, propyl-ethyl sulphide, dibenzyl sulphide, diphenyl sulphide, e

Thus, by condensing an organic sulphide with a halogenated, hydrocarbonaceous material of the aforementioned group, sulphonium halides are obtained, having the structure:

in which P represents a petroleum hydrocarbon chain. If P is a chain containing eight or more carbon atoms the sulphonium halide becomes cation-active and an incrustation inhibitor. Cation-active compounds are surface-active compounds which carry in the cation a hydrocarbon chain having eight or more carbon atoms. They are particularly advantageous because they may be used in neutral (salt), alkaline and acidic' aqueous solutions; and also in hard water. In contradistincti'on to cation-active compounds, anion-active compounds are surface-active com pounds which carry in the anion a more or less They flocculate in neutral (salt), alkaline and acidic aqueous solutions, and also in hard water. Common soaps, sulphonated oils, salts of sulphonated fatty acids, etc., are examples of anion-active compounds, and they are unable to prevent the incrustation oi spinnerets and spinneret holes. These incrustation inhibitors are prepared by heating a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums, and paraflln waxes with an organic sulphide at a moderate temperature-preferably under refluxuntil condensation is completed. Before heating the two components they may be dissolved in a suitable, inert solvent, such as, for example, benzene, ether, toluene, etc., i. e., in solvents which are incapable of chemically reacting with the compounds to be condensed. The inert solvent may subsequently be removed from the condensation products by distillation, and the unreacted sulphide may be separated from the condensation products by distillation, extraction, etc. The crude incrustation inhibitors may contain a number of different condensation products which need not be separated from each other. In other words, the crude condensation products (incrustation inhibitors) containing cation-active and cation-inactive constituents may, for reasons of economy, he added without further purification to viscose solutions or spin baths (setting baths). Although these cation-active halides, i. e., bromides, chlorideaiodides and fluorides, may form sulphonium bases in viscose solutions and sulphonium salts in acid spin baths, they retain their surface-activity and, thus, their property of preventing incrustations. If very small amounts of these condensation products are added to viscose solutions or spin baths the physical characteristics, such as strength, plasticity, $5

from the group consisting of crude ucts. In other words, these additions are critical and their amounts must be predetermined by experimentation. Additions of about 0.4 to 1.0 gram per liter of viscose or spin bath are insuflicient to substantially alter the physical characteristics of regenerated cellulose although they allow continuous spinning for long periods of time.

Although these cation-active sulphonium compounds improve the spinning properties of any conventional viscose solution or any spin bath known in the art, I have found that they are especially valuable additions to zinc-bearing baths which tend to interrupt spinning, i. e., spin baths containing zinc compounds, such as, for example, zinc sulphate.

Example 1 ,EthyLmethyl sulphide is condensed with a halogenated, hydrocarbonaceous material selected petroleums, kerosenes, gasolines, lubricating oils, pasty petrolatums, liquid petrolatums and paraflln waxes by heating under reflux until condensation is completed. About 0.4 to 1.0 gram of the condensation products are added to one liter of a viscose solution voi conventional cellulose content and maturity. This solution is then spun into a conventional, acid spin bath, such as, for example, a glucose bath, a magnesium-zinc bath, etc. The spinnerets and spinneret holes remain clean on prolonged spinning in comparison with the spin bath free from cation-active compounds. Any dialkyl sulphide, diaryl sulphide or alkylaryl sulphide may be used in the condensation, which may be carried out at any temperature at which the two reactants and remain stable.

Example 2 An alkyl-aryl sulphide, a dialkyl sulphide or a diary] sulphide, such as, for example, dibenzyl sulphide is condensed with a halogenated paraffin wax in the presence of an inert solvent, such as, for example, benzene, etc., under substantially anhydrous conditions. A conventional viscous solution is extruded through fine orifices of a spinneret of a precious metal into an acid spin bath, this bath containing sulphuric acid, sodium sulphate, ammonium sulphate and zinc sulphate plus about 0.05% by weight of a cation-active substance set forth above. Spinning irregularities and difiiculties are substantially overcome while withourl: this inhibitor spinning is interrupted after a very short period of time. These inhibitors are especially suitable for continuous spinning processes using sulphuric acid-zinc sulphate baths. These sulphides may be condensed with any halogenated, hydrocarbonaceous material of the group set forth above.

Example 3 Cation-active condensation products are added to both the viscose solutions and thespin baths the sulphonium halide to allow continuous formation of lustrous or softlustre viscose'products.

Although these examples will serve to illustrate the present invention. I do not wish to be limited to the inhibitors and concentrations thereof re- I cited therein, since I may use any cation-active sulphonium compound of the group set forth above and vary the physical characteristics of regenerated cellulose by varying their amounts in viscose solutions and/or spin baths, provided these inhibitors. are su'mciently soluble in viscose solutions and/or spin baths to furnish cations therein.

Modifications of myv invention will readily be recognized by those skilled in the art, and I desire to include all such modifications and variations coming within the scope of the appended claims.

' I claim:

1. A spin bath, adapted for use in the manuiacture oi regenerated cellulose, containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolaturns and paraffin waxes and an organic sulphide, said condensation product being sufficiently soluble and stable in said setting bath to become cation-active therein.

2. A spin bath, adapted for use in the manufac- {ture of regenerated cellulose, containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflin waxes and a dialkyl sulphide, said condensation product being suillciently soluble and stable in said setting bath to become cation-active therein.

3. A spin bath, adapted for use in the manufacture of regenerated cellulose, containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraffin waxes and an alkylaryl sulphide, said condensation product. being suiliciently soluble and stable in said setting bath to become cation-active therein.

4. A spin bath, adapted for use in the manufacture of regenerated cellulose, containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflin waxes and a diaryl sulphide, said condensation product being sufilciently soluble and stable in said setting bath to become cation-active therein.

5. A spin bath, adapted for use in the manufacture of regenerated cellulose, containing about 0.4 to 1.0 gram per liter of a cation-active condensation product of a chlorinated parailin wax and an ethyl-methyl sulphide.

6. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water-soluble zinc compound and about 0.4 to 1.0 gram per liter of said bath of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraffin waxes with an organic sulphide. said condensation product being .sufllciemtly soluble and stable in said bath to become cation-active there- 7. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water-soluble zinc compound and about 0.4 to 1.0 gram per liter of said bath of a cation-active condensation product oi! a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflln waxes with a dialkyl sulphide, said condensation product being sumcient- 1y soluble and stable in said bath to become cation-active therein.

8. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water-soluble zinc compound andabout 0.4 to 1.0 gram per liter of said bath of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflin waxes with an alkyl-arylsulphide, said condensation product being sufficiently soluble and stable in said bath to become cation-active therein.

9. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water-soluble zinc compound and about 0.4 to 1.0 gram per liter of said bath of a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and parafiln waxes with a diaryl sulphide, said condensation product being sufiicient- 1y soluble and stable in said bath to become cation-active therein.

10. A spin bath adapted to be used in the manuiacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zinc compound and about 0.4to 1.0 gram per liter of said bath of a cation-active condensation product of a chlorinated paraflln wax and ethyl-methyl sulphide.

11. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid,'- a watersoluble zinc compound and a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paraflin waxes with an organic sulphide, said condensation product being sufllcient- 1y soluble and stable in said bath to become cation-active therein.

12. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a watersoluble zinc compound and a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums, gasolines, kerosenes, lubricating oils, pasty petrolatums, liquid petrolatums and paramn waxes with a dialkyl sulphide, said condensation product being sufllciently soluble and stable in said bath to become cation-active therein.

13. A spin bath adapted to be used in the manufacture of regenerated cellulose from viscose solutions comprising sulphuric acid, a water soluble zinc compound and a cation-active condensation product of a halogenated hydrocarbonaceous material selected from the group consisting of crude petroleums. gasolines, kerosenes, lubricating oils, pasty petrolatuma. liquid petrolatums, and paraflln waxes with an alkyl-aryl sulphide,=said condensation product being' lulticiently soluble and stable in said bath to become cation-active therein.

RUDOLPH s. am 

